Synthesis of comb-shaped polyvinylthiophenes with anionic polymerization of 5-vinyl-2,2′-bithiophene (VBT) and Suzuki-Miyaura cross-coupling reaction of Poly(VBT): Control of intermolecular interactions of adjacent side chains

• Published in: Polymer (Guilford) Vol. 210; p. 122997
• Main Authors: Natori, Itaru, Natori, Shizue, Hanawa, Naoki, Nakamura, Akitaka, Taehee, Jahg, Ogino, Kenji
• Format: Journal Article
• Language: English
• Published: Kidlington Elsevier Ltd 01.12.2020; Elsevier BV
• Subjects: Anionic polymerization; Bromination; Chemical reactions; Chemical synthesis; Comb-shaped; Cross coupling; Optical properties; Organic solvents; Polymerization; Polymers; Polyvinylthiophenes; Solubility; Thin films; Anionic polymerization; Comb-shaped; Polyvinylthiophenes
• ISSN: 0032-3861; 1873-2291
• DOI: 10.1016/j.polymer.2020.122997

Soluble comb-shaped polyvinylthiophenes with well-controlled and defined multifunctional side chains were synthesized for the first time. Poly(5-vinyl-2,2′-bithiophene) (PVBT) as a main chain was obtained successfully by a thoughtfully designed anionic polymerization of 5-vinyl-2,2′-bithiophene. Bromination and Suzuki-Miyaura cross-coupling of PVBT gave the desired multifunctional side chains in almost quantitative yield. The obtained polymers could be quickly and easily purified by reprecipitation. The insertion of a repelling unit in the side chain prevented strong π-π interactions between adjacent side chains and dramatically improved the solubility of the comb-shaped polyvinylthiophenes. The optical properties of these polymers were strongly influenced by the intermolecular interactions of adjacent side chains. These comb-shaped polyvinylthiophenes possessed good solubility in common organic solvents, adjustable optical (or electrical) properties, and the ability to form high-quality thin films. [Display omitted] •Soluble comb-shaped polyvinylthiophenes with well-controlled and defined side chains were synthesized for the first time.•Poly(5-vinyl-2,2′-bithiophene) (PVBT) was obtained successfully by a thoughtfully designed anionic polymerization.•The optical properties of these polymers were strongly influenced by the intermolecular interactions of adjacent side chains.•Soluble comb-shaped polyvinylthiophenes possessed adjustable optical (or electrical) properties.